Process for inhibiting foam



United States Patent G i PROCESS FOR INHIBITING FOAM Louis T. Monson,Puente, Califi, assignor to Petrolitc Corporation, a corporation ofBahia are No Drawing. Application December 18, 1951, Serial No. 262,322

14 Claims. (Cl. 252-321) In my co-pending application, Serial No.180,691, filed August 21, 1950, now Patent No. 2,622,069, issuedDecember 16, 1952, I have disclosed and claimed a process for inhibitingfoam in which hydrophile oxyalkylated syn thetic resins are employed.

I have now made what amounts to an invention within the broadest aspectsof that invention, in that I have discovered that a particular sub-genusof the genus of hydrophile oxyalkylated synthetic resins is especiallyeffective in reducing or destroying foam or preventing its formation, incompositions of either aqueous or nonaqueous character.

Foams occur as undesirable, incidental features in many industrialprocesses. The theory of their formation is not highly developed; sothat hypotheses on which foam reduction or destruction processes mightbe based are difficult to formulate. As a consequence, foam-destroyingagents are usually devised for use in the case of particular foams.

.I have discovered a novel process of reducing or destroying foams andof preventing their formation, which appears to be relatively general inapplicability, in that it may be used on compositions comprising aqueousmaterials or solutions; on compositions comprising non-aqueousmaterials, such as hydrocarbon liquids; and on compositions comprisingmixtures of aqueous and non-aqueous media. My process consists insubjecting a foaming or potentially-foaming composition to the action ofa small proportion of a reagent or anti-foamer of the kind subsequentlydescribed, thereby causing the foaming properties of the liquid to bediminished, suppressed or destroyed. In applying my process to thereduction or destruction of a foam, the reagent may be poured or sprayedor dripped into the body of foam on top the liquid, as desired; and thefoam breaks and is destroyed or reduced, substantially at once, as aconsequence of such addition of said reagent. Adding the reagent to theliquid underlying such already-formed foam is also practicable. Inapplying my process to the prevention of foaming, the reagent isadmixed, in some small proportion, with a potentially-foaming liquid, byany desired or suitable procedure. The ability of the system to foam isdestroyed or at least materially reduced by such addition of saidreagent.

Reference is made to United States Patent No. 2,499,- 370, to De Grooteand Kei ser, dated March 7, 1950, wherein, for use as demulsifiers forpetroleum emulsions, certain hydrophile oxyalkylated synthetic resinsare claimed. The reagents of the present invention lie Within the classof reagents described in said patent. They are characterized by the factthat at least one-half by weight of the oxyalkylated synthetic resinconsists of the element (CsHsOM, wherein Cal-Is is the propyleneradical. Stated 2 ,748,087 Patented May 29, 1956 One or more of theother alkylene oxides, ethylene oxide, butylene oxide, hydroxypropyleneoxide (glycid) or hydroxybutylene oxide (methylglycide), may be presentin my reagent. In some instances, incorporation of the optimumproportion of such other alkylene oxide acts to raise the effectivenessof my already highly elfective reagent to an even higher level ofperformance.

My process is therefore a process for inhibiting foam, characterized bysubjecting a foaming composition to the action of a reagent including ahydrophile oxyalkylated 2,4,6 C4- to Cm-hydrocarbon-substitutedmonocyclic phenol-C1- to Cs-aldehyde resin; the alkylene radicals of theoxyalkylene groups being selected from the class consisting of ethylene,propylene, butylene, hydroxypropylene, and hydroxybutylene radicals;with the proviso that at least one-half by weight of said oxyalkylatedresin consist of a multiple of the divalent oxypropylene group, CsHsO.

More precisely expressed, mine is a process for inhibiting foam,characterized by subjecting a foaming composition to the action of areagent including hydrophile synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) an alpha-betaalkylene oxide having not more than 4- carbon atoms and selected fromthe class consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide, and (B) an oxyalkylation-susceptible,fusible, organic-solvent-soluble, water-insoluble phenol-aldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol, said resin being formed in the substantial absenceof phenols of functionality greater than two; said phenol being of theformula in which R is a hydrocarbon radical having at least 4 and notmore than 14 carbon atoms and substituted in the 2,4,6 position; saidoxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent radicals having the formula(R10)n, in which R1 is a member selected from the class consisting ofethylene radicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and hydroxybutylene radicals; n being anumeral of such size that at least onehalf by weight of saidoxyalkylated resin consists of a multiple of the divalent oxypropylenegroup, CaHeO.

Stated in still greater detail, the hydrophile properties of saidoxyalkylated resin are sufiicient to produce an emulsion when saidoxyalkylated resin is dissolved in an equal Weight of xylene and saidxylene solution is shaken vigorously with from one to three volumes ofwater. The resin is preferably a low-stage resin having an averagemolecular weight corresponding to from 3 to 7 phenolic nuclei per resinmolecule; the aldehyde is preferably an aliphatic aldehyde, and mostpreferably formaldehyde; and the resinification reaction is preferablyacid-catalyzed. I incorporate into this present application by referencethe 103 a examples of alkylphenol-aldehyde resins set out in Patent No.2,499,370. These may be employed as starting materials to produce theoxyalkylated derivatives employed in my process. Most of the b examplesof said patent relate to oxyethylated derivatives of such resins; butExamples 2b and 11b relate to oxypropylated derivatives of the presentclass; and I incorporate them into this application by reference.

Example 2b of the above-mentioned U. S. Patent No. 2,499,370 calls forthe oxypropylation .of grams of butylphenol-formaldehyde resin with 400grams of pro pylene oxide, following the procedure outlined in Example1b of said patent. The product of Example 2b of said patent is thereforean example of the present class of materials.

Likewise, Example 11b of said patent calls for the oxypropylation of theparadodecylphenol-formaldehyde resin of Example 74a of that patent,using 600 grams of propylene oxide and 170 grams of resin, and theoxyalkylation procedure of Example 1b of the patent. The prodnot ofExample 11b of said patent is therefore an example of the present classof materials.

Additional examples of the preparation of materials Suitable for use inmy present process are given below.

Example 1 Use the para-tertiary amylphenol-formaldehyde resin of Example3a of U. S. Patent No. 2,499,370, to De Groote and Keiser. To 350 gramsof said resin, mixed with 350 grams of commercial aromatic petroleumsolvent, add 20 grams of sodium hydroxide in the form of a 50% aqueoussolution, in a conventional stirring autoclave. Heat the mixture toevaporate the water of solution. Then seal the autoclave, raise thetemperature to about 125 C., and pass in propylene oxide until a totalof 500 grams has been introduced.

Example 2 To the finished product of Example 1 above, still in theautoclave, add 75 grams of ethylene oxide in a slow, continuous stream,at a temperature about 165 C., avoiding development of any pressureabove about 50 p. s. i. g.

Example 3 Repeat Example 1 above using the amylphenol-glyoxal resin ofExample 13a of above-mentioned U. S. Patent No. 2,499,370 instead of theamylphenol-formaldehyde resin, employing the same Weights of resin andpropylene oxide as in Example 1 above.

Example 4 To the finished product of Example 3 above, still in theautoclave, introduce 100 grams of ethylene oxide in a slow, continuousstream, at a temperature of about 165 C., avoiding development of anypressure above about 50 p. s. i. g.

Example 5 Repeat Examples 1 and 2 above, using the paratertiarybutylphenol-acetaldehyde resin of Example 14a of abovementioned U. S.Patent No. 2,499,370, and the weights and conditions of Examples 1 and 2above.

Example 6 Use 350 grams of the nonylphenol-formaldehyde resin of Example70a of above-mentioned U. S. Patent No. 2,499,370 instead of theamylphenol-forrnaldehyde resin of Examples 1 and 2 above. Use theweights and conditions of Examples 1 and 2 above.

Example 7 Into the xylene solution of oxypropylated product of Example 7above, introduce 125 grams of ethylene oxide at a temperature of about165 C. and a pressure not exs sj ns 5 1H1 Example 9 Prepare atetradecylphenol-formaldehyde resin from commercial grade C14alkylphenol and formaldehyde, in conventional manner. To 500 grams ofthis resin and 500 grams xylene, add 30 grams of sodium hydroxide, inaqueous solution. Distill off the water of solution, in a conventionalstirring autoclave. Seal the autoclave and pass in 800 grams ofpropylene oxide at a temperature of 150 C., regulating the flow ofalkylene oxide to'maintain a. pressure of not more than 50 p. s. i. g.

Example 10 Into the xylene solution of oxypropylated product of Example9 above, introduce 200 grams of ethylene oxide at a temperature of about165 C. and a pressure not exceeding 50 p. s. i. g.

Example 11 To 350 grams of the resin of Example 1 above add 150 grams ofglycid, at about C., in the presence of 25 grams of sodium hydroxide,introducing the glycid in small portions and permitting dissipation ofany temperature increase before adding the next portion of the oxyakylating agent. Then proceed with the oxypropylation as in said Example1 above, but using a total of 650 grams of propylene oxide.

Example 12 Use 500 grams of the resin of Example 9 above. Be foreproceeding with the oxypropylation as in said example, introduce gramsof butylene oxide at a temperature of about 170 C. Then proceed with theaddition of propylene oxide as in said Example 8 above, using a total of800 grams of propylene oxide.

Example 13 Substitute methylglycid for glycid in Example 11 above, gramfor gram, using the other reactants, and the conditions of said Example11.

Example 14 Add 75 grams of ethylene oxide to the oxypropylated productof Example 13 above, using a temperature of about C. and a pressure notexceeding 50 p. s. i. g.

In the foregoing examples, Where no addition of ethylene oxide wasspecified, it is of course possible to introduce such alkylene oxide,just as was illustrated by Examples 2 and 4 above.

In oxypropylating the various resinous starting materials,

it will usually be found that reaction is not as readily achieved aswould be oxyethylation. The directions given in the aforementioned DeGroote and Keiser patent relate mostly to oxyethylation. Thosedirections may be translated to oxypropylation if the lesser reactivityof propylene oxide is recognized. in other words, oxypropylation usuallyrequires a higher temperature than oxyethylation if it is to beaccomplished in the same time; or, conversely, at a given temperature,oxypropylation requires a longer time than oxyethylation. Oxyalkylationprocedures are so well-known that it is unnecessary to do more thanstate that oxyalkylation is conducted by conventional procedures, toproduce the reagents of the present process. As a preferred example ofmy present class of foam inhibitors, the following may be recited:

Charge into a stirring autoclave 50 grams of an amylphenol-formaldehyderesin, of conventional character, e. g., that of Example 3a of U. S.Patent No. 2,499,370, and 50 grams of commercial aromatic petroleumsolvent. Introduce 6 grams of sodium hydroxide in the form of a 50%aqueous solution. Heat until the water of solution is substantiallycompletely removed, with stirring. Seal the autoclave, purge withnitrogen, and introduce 850 grams of propylene oxide at a temperature ofabout 120 C., maintaining a pressure of less than about 20 p. s. i. g.Thereafter, introduce 100 grams of ethylene oxide at about 165 C. Dilutethe product with 1450 grams more of aromatic petroleum solvent. Theresulting product is suitable for use as a foam inhibitor.

This preferred example illustrates the fact that my reagents may includeoxyalkylene groups derived or derivable from alkylene oxides other thanpropylene oxide. Such other oxyalkylene groups may be introduced intothe molecule either before or after the introduction of the oxypropylenegroup; and in most instances it is possible to introduce themsimultaneously. For example, one may oxyalkylate with a mixture ofethylene oxide and propylene oxide, both oxides being absorbed by theoxyalkylation-susceptible synthetic resin.

My present class of oxyalkylated resinous derivatives may be used alonein foam inhibition, or they may be used in admixture with any othereifective and compatible anti-foamer, e. g., with the reagents describedand claimed in my U. S. Patent No. 2,408,527, dated October 1, 1946,those described and claimed in my co-pending application, Serial No.775,145, filed September 19, 1947, now Patent 2,622,070, grantedDecember 16, 1952, or those described and claimed in my co-pendingapplication, Serial No. 180,691, filed August 21, 1950, now Patent2,622,069, granted December 16, 1952.

It is usually convenient 'to dilute my reagents during manufacture orbefore use with some suitable solvent. Solvents generally suitable forincorporation into my reagent include: water; petroleum hydrocarbons,like gasoline, kerosene, stove oil, aromatic solvent; coal tar products,such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil;alcohols, particularly aliphatic alcohols like methyl, ethyl, isopropyl,butyl, hexyl, octyl, etc. Miscellaneous solvents, such as pine oil,carbon tetrachloride, etc., may be employed. Sometimes other factorssuch as whether it imparts an objectionable odor .to the defoamedcomposition or to the products into which it finds its way willdetermine the choice of solvent. In general, the amounts of finishedanti-foamer reagent employed are so small that considerable tolerance ofundesirable properties in a solvent exists.

The mixture of active ingredients and solvents is stirred untilhomogeneous. I prefer to employ a petroleum distillate in the proportionof to 50% of the finished product, by volume, although water is anexcellent solvent in some instances.

I desire to point out that the superiority of the reagent contemplatedin my process is based upon its ability to reduce or destroy foam, or toprevent foam formation, in certain foaming or potentially foamingcompositions more advantageously and at lower cost than is possible withother reagents or processes. In certain instances, it has been found todestroy or reduce foams or prevent their formation, which foams were noteconomically or effectively reducible or preventable by any-other knownmeans.

My reagents are useful in controlling foams in many different types ofsystem, aqueous and non-aqueous. They will control foams encountered inthe manufacture of alkaline hypochlorite bleaches. They are effective incontrolling foam in petroleum refining operations. They are effective ininhibiting foam in a gas-treating system, in which a mixture of glycolsand alkanolamines is used to dehydrate and purify natural gas.

I have applied my reagents to the control of foam in protein adhesivessolutions, such as casein and soybean adhesives, as used in the plywoodindustry. Latex adhesives, printing inks, aqueous emulsion paints, allproduce foams which are amenable to my reagents.

In the foregoing description, I have made 'it clear that my reagents maybe used to reduce, destroy, or prevent 6 eral techniques commonlyemployed. It should be understood that the claims are not limited to theprocedures described; and that my process consists broadly in bringinginto contact by any suitable means my reagent and the foam or thepotentially foaming composition.

in controlling foam in a glycol-amine gas treating plant handlingnatural gas, the glycol-amine mixture had a volume of about 2,000gallons and make-up was about 2,000 gallons a month. My preferredreagent was injected into the liquid mixture in the return line from thestripping operation, by means of an electricallypowered proportioningpump of conventional design. The feed rate was less than 1 quart daily.Foam difiiculties in the system were satisfactorily controlled by thisprocedure.

In sewage plants, for example, in activated-sludgeprocess plants, foamis frequently a serious problem in aeration basins and elsewhere. In onesuch plant, I have demonstrated that my reagent will control foam whensprayed into the head of foam, or when sprayed into or simply pouredinto the liquid in such basin. The foaminhibiting effect appears topersist quite satisfactorily.

Determination of the optimum or minimum amount of my foam-inhibitingreagent to be used in any application may be accomplished in differentways. Small portions of the potentially foaming liquid may be filledinto test bottles, different small proportions of my reagent added, andthe chemicalized samples shaken for a short time. Simple observation ofthe relative speed and completeness of foam destruction should permitselection of the best reagent proportion to be applied on the largescale. The easiest way to determine the amount of my reagent required isto introduce it into the foaming or potentially foaming liquid in afairly large proportion, e. g., 1%, and then to reduce the reagent feedrate until foam destruction is just being accomplished satisfactorily.Usually foam destruction is directly proportional to the amount ofreagent used, at least up to about 1% of reagent. In a few instances, itmay be found that using more or less reagent than an optimum proportionwill give inferior results.

If the proportions of reagent to be employed in the above test are verysmall, it may be desirable to determine the optimum proportions offoaming composition and anti-foarner by introducing the latter into thesample of foaming liquid in the form of a solution in a suitablesolvent.

Throughout this specification, I have shown that my process is eguallyapplicable to systems in which a foam is already in existence and tosystems which are potentially foaming compositions, in that they havethe property of producing foams when agitated or mixed with air or someother suitable gas. Destruction, reduction and prevention aresubstantially equivalent actions. It is impossible to determine whetherthe reagent does in fact prevent the formation of the initial laminae offoam or whether such initial laminae are destroyed by the reagent beforesubsequent laminae of sufficient stability to produce a foam can besuperimposed thereon. By foaming composition in the appended claims, Imean a composition which is either actually foaming or which is capableof producing a foam under suitable conditions, e. g., by simply passingair through it.

In most instances, my reagent is eifective to the extent that itdestroys an existing foam substantially completely. In some instances,as when too little reagent is used, foam reduction may be slow or evenincomplete. I intend that this description and my invention relate bothto complete destruction and to partial destruction of foams.

The proportions of my reagent required to be employed appear to varywidely. However, I wish to limit my invention to the use of my reagentin amounts 1% or less of the foaming composition. Usually, the amountsrequired will be between 0.1% and 0.0001%.

I have stated above that my present reagents may be used in conjunctionwith any other effective and com- .patible anti-foamer. It should alsobe stated that they are useful in conjunction with foam-inhibitingprocesses which are mechanical or electrical in character, rather thanchemical. For example, some foams may be effectively destroyed by watersprays or jets. Incorporation of a small proportion of my reagents intosuch water sprays increases their effectiveness. U. S. Patent No.2,240,495, to Dillon et al., dated May 6, 1941, relates to a process forresolving foam by means of a high electrical potential. Incorporation ofa small proportion of my present reagents into the foaming liquidincreases the effectiveness of such electrical processes.

; Having thus described my invention, what I claim as novel and desireto secure by Letters Patent is:

l. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile oxyalkylated 2,4,6 04- to Cit-hydrocarbon-substitutedmonocyclic phenol C1- to Cit-aldehyde resin; the alkylene radicals ofthe oxyalkylene groups being selected from the class consisting ofpropylene and mixtures of ethylene and propylene radicals; with theproviso that at least one-half by weight of said oxyalkylated resinconsist of a multiple of the divalent oxypropylene group, C3HsO.

2. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) an alpha-beta alkylene oxide selected fromthe class consisting of propylene oxide and mixtures of ethylene andpropylene oxides, and (B) an oxyalkylation-susceptible, fusible,organic-solvent-soluble, waterinsoluble phenolaldehyde resin; said resinbeing derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and reactive toward saidphenol, said resin being formed in the substantial absence of phenols offunctionality greater than two; said phenol being of the formula inwhich R is a hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; said oxylalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R)n, in which R1 isa member selected from the class consisting of propylene radicals andmixtures of ethylene and propylene radicals; n being a numeral of suchsize that at least one-half by weight of said oxyalkylated resinconsists of a multiple of the divalent oxypropylene group, CsHsO.

3. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) an alpha-beta alkylene oxide selected fromthe class consisting of propylene oxide and mixtures of ethylene andpropylene oxides, and (B) an oxyalkylation-susceptible, fusible,organic-solvent-soluble, water-insoluble phenol-aldehyde resin; saidresin being derived by reaction between a difunctional monohydric phenoland an aldehyde having not over 8 carbon atoms and reactive toward saidphenol; said resin being formed in the substantial absence of phenols offunctionality greater than two; said phenol being of the formula inwhich R is a hydrocarbon radial having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule of,a plurality of divalent radicals having the formula (R10)n in which R1is a member selected from the class consisting of propylene radicals andmixtures of ethylene and propylene radicals; n being a numeral of suchsize that at least one-half by weight of said oxyalkylated resinconsists of a multiple of the divalent oxypropylene group, CsHsO; withthe final proviso that the hydrophile properties of said oxyalkylatedresin in an equal weight of xylene are sufficient to produce an emulsionwhen said xylene solution is shaken vigorously with one to three volumesof water.

4. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) an oxyalkylation-susceptible, fusible, organic-solvent-soluble,water-insoluble phenol-aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of phenols of functionalitygreater than two; said phenol being of the formula in which R is ahydrocarbon radical having at least 4 and not more 14 carbon atoms andsubstituted in the 2,4,6 position; said oxyalkylated resin beingcharacterized by introduction into the resin molecule of a plurality ofdivalent groups having the formulas (C2H40)n and (C3H60)n', where n andn are numerals of such size that at least one-half by weight of saidoxyalkylated resin consists of a multiple of the divalent oxypropylenegroup, CsHsO; with the final proviso that the hydrophile properties ofsaid oxyalkylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

5. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) an oxyalkylation-susceptible, fusible, organic-solvent-soluble,water-insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight corresponding to at least 3 and not over 7 phenolicnuclei per resin molecule; said resin being derived by reaction betweena di-functional monohydric phenol and an aldehyde having not over 8carbon atoms and reactive toward. said phenol; said resin being formedin the substantial absence of phenols of functionality greater than two;said phenol being of the formula in which R is a hydrocarbon radicalhaving at least 4 and more than 14 carbon atoms and substituted in the2,4,6 positions; said oxyalkylated resin being characterized by theintroduction into the resin molecule of a plurality of divalent groupshaving the formulas (C2H40)n and (C3HGO)7I,', wherein n and n arenumerals of such size that at least one-half by weight of saidoxyalkylated resin consists of a multiple of the divalent 9 oxypropylenegroup, CsHeO; with the final proviso that the hydrophile properties ofsaid oxyalkylated resin in an equal weight of xylene are sufficient toproduce an emulsion when said Xylene solution is shaken vigorously withone to three volumes of water.

6. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) an oXyalkylation-susceptible, fusible, organic-solvent-soluble,water-insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight corresponding to at least 3 and not over 7 phenolicnuclei per resin molecule; said resin being derived by reaction betweena difunctional monohydric phenol and an aldehyde having not over 8carbon atoms and reactive toward said phenol; said resin being formed inthe substantial absence of phenols of functionality greater than two;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; said oxyalkylated resin beingcharacterized by introduction into the resin molecule of a plurality ofdivalent groups having the formulas (C2H4O)n and (C3H60)n, wherein n andn are numerals of such size that at least one-half by Weight of saidoxyalkylated resin consists of a multiple of the divalent oxypropylenegroup, CsHeO; with the final proviso that the hydrophile properties ofsaid oxyalkylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes or" water.

7. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) an oxyalkylation-susceptible, fusible, organic-solvent-soluble,water-insoluble, low-stage phenolaldehyde resin having an averagemolecular weight corresponding to at least 3 and not over 7 phenolicnuclei per resin molecule; said resin being derived by reaction betweena difunctional monohydric phenol and an aliphatic aldehyde having notover 8 carbon atoms and reactive toward said phenol; said resin beingformed in the substantial absence of phenols of functionality greaterthan two; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 14 carbon atomsand substituted in the 2,4,6 position; said oxyalkylated resin beingcharacterized by introduction into the resin molecule of a plurality ofdivalent groups having the formulas (C2H40)n and (CsHsOhv, wherein n andn are numerals of such size that at least one-half by weight of saidoxyalkylated resin consists of a multiple of the divalent oxypropylenegroup, CsHsO; with the final proviso that the hydrophile properties ofsaid oxyalkylated resin in an equal Weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

'8. A'process forinhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) oXyalkylation-susceptible, fusible, organic-sob vent-soluble,water-insoluble, low-stage phenol-formaldehyde resin having an averagemolecular Weight corresponding to at least 3 and not over 7 phenolicnuclei per resin molecule; said resin being derived by reaction betweena difunctional monohydric phenol and formaldehyde; said resin beingformed in the substantial absence of phenols of functionality greaterthan two; said phenol being of the formula in which R is an aliphatichyrocarbon radical having at least 4 and not more than 14 carbon atomsand substituted in the 2,4,6 position; said oxyalkylated resin beingcharacterized by the introduction into the resin molecule of a pluralityof divalent groups having the formulas (Chi-%; and (C3H60)n', wherein nand n are numerals of such size that at least one-half of saidoxyalkylated resin consists of a multiple of the divalent oxypropylenegroup, CsHsO; with the final proviso that the hydrophile properties ofsaid oxyalkylated resin in an equal weight of xylene are sufficient toproduce an emulsion when said Xylene solution is shaken vigorously withone to three volumes of water.

9. A process for inhibiting foam, characterized by subjecting anon-detersive foaming composition to the action of not more than 1% of ahydrophile synthetic product; said hydrophile synthetic product being anoxyalkylation product of (A) ethylene oxide; (B) propylene oxide; and(C) an oxyalkylation-susceptible, fusible, organic-solvent-soluble,water-insoluble, low-stage, acid-catalyzed phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 7 phenolic nuclei per resin molecule; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of phenols offunctionality greater than two, said phenol being of the formula inwhich R is an aliphatic hydrocarbon radical having at least 4 and notmore than 14 carbon atoms and substituted in the 2,4,6 position; saidoxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent groups having the formulas(C2H4Q)n and (C3H60)n', wherein n and n are numerals of such size thatleast one-half by Weight of said oxyalkylated resin consists of amultiple of the divalent oxypropylene group, CBHGO; With the finalproviso that the hydrophile properties of said oxyalkylated resin in anequal Weight of xylene are sufficient to produce an emulsion when saidXylene solution is shaken vigorously with one to three volumes of water.

10. The process of claim 9, wherein R is a butyl radical.

11. The process of claim 9, wherein R is an amyl radical.

1 1 12 S v 12. The process of claim 9, wherein R is an octyl radi-References Cited in the file of this patent cal. UNITED STATES PATENTS3. Th 9, h R 1 (1'- call. 6 Pmcess dam w a m 1 2,454,541 Beck et a1.Nov. 23, 1948 14. Th h R t t d 5 2,454,544 Bock et a1 NOV. 23, 19 8:radicaL e Pwcess 9 W a e ta ecyl 2,557,081 De Groote et a1 June 19,1951

1. A PROCESS FOR INHIBITING FOAM, CHARACTERIZED BY SUBJECTING ANON-DETERSIVE FOAMING COMPOSITION TO THE ACTION OF NOT MORE THAN 1% OF AHYDROPHILE OXYALKYLATED 2,4,6 C4- TO C14-HYDROCARBON-SUBSTITUTEDMONOCYCLIC PHENOLC1-C8-ALDEHYDE RESIN; THE ALKYLENE RADICALS OF THEOXYALKYLENE GROUPS BEING SELECTED FROM THE CLASS CONSISTING OF PROPYLENEAND MIXTURES OF ETHYLENE AND PROPYLENE RADICALS; WITH THE PROVISO THATAT LEAST ONE-HALF BY WEIGHT OF SAID OXYALKYLATED RESIN CONSIST OF AMULTIPLE OF THE DIVALENT OXYPROPYLENE GROUP, C3H6O.